WO2014010681A1

WO2014010681A1 - Collector, electrode structure, nonaqueous electrolyte cell, and electricity storage component

Info

Publication number: WO2014010681A1
Application number: PCT/JP2013/069008
Authority: WO
Inventors: 加藤　治; 泰正盛島; 貴和伊藤; 英和原; 恭宏飯田; 片岡　次雄; 光哉井上; 郷史山部; 幸翁本川; 聡平斉藤; 起郭八重樫
Original assignee: 古河電気工業株式会社; 日本製箔株式会社; 古河スカイ株式会社
Priority date: 2012-07-13
Filing date: 2013-07-11
Publication date: 2014-01-16
Also published as: EP2874213A1; JPWO2014010681A1; CN104428929B; TW201414069A; EP2874213B1; CN104428929A; EP2874213A4; KR20150032335A; US20150294802A1

Abstract

Provided is a collector having a PTC layer having leeway for thermal expansion during an increase in temperature while ensuring sufficient electroconductivity at regular temperatures. According to the present invention, there is provided a collector comprising an electroconductive substrate and a resin layer provided to at least one surface of the electroconductive substrate. The resin layer includes an organic resin and electroconductive particles. The amount of resin layer adhering on the electroconductive substrate is 0.5 to 20 g/m². The Rz (ten-point average roughness) of the surface of the resin layer is 0.4 to 10 μm. The Sm (average interval between concavities and convexities) of the surface of the resin layer is 5 to 200 μm. The average of the resistance of the resin layer, measured by the two-terminal method, is 0.5 to 50 Ω.

Description

Current collector, electrode structure, non-aqueous electrolyte battery or power storage component

The present invention relates to a current collector, an electrode structure, a nonaqueous electrolyte battery, or a power storage component.

Due to the high energy density, the use of lithium batteries in electronic devices such as mobile phones and laptop computers is expanding. In the lithium battery, lithium cobaltate, lithium manganate, lithium iron phosphate and the like are used as the positive electrode active material, and graphite is used as the negative electrode active material. A lithium battery is generally composed of an electrode made of these active materials, a separator that is a porous sheet, and an electrolyte solution in which a lithium salt is dissolved. Such a lithium secondary battery has a high battery capacity and output, good charge / discharge characteristics, and a relatively long service life.

リチウム Lithium batteries have the advantage of high energy density, but have a problem with safety because they use non-aqueous electrolyte. For example, since the non-aqueous electrolyte is included, the components of the non-aqueous electrolyte are decomposed as the heat is generated, so that the internal pressure increases and the battery may swell. Moreover, when the lithium secondary battery is overcharged, there is a possibility that problems such as heat generation may occur. Further, there is a possibility that problems such as heat generation may occur due to the occurrence of an internal short circuit.

As means for improving the safety of the battery, there are prevention of an increase in internal pressure by a safety valve, current interruption at the time of heat generation by incorporating a PTC (Positive temperature coefficient) element whose resistance value increases as the temperature rises. For example, a method of attaching a PTC element to a positive electrode cap portion in a cylindrical battery is known.

However, the method in which the PTC element is attached to the positive electrode cap portion has a problem that an increase in the short circuit current cannot be suppressed when an internal short circuit occurs and the temperature rises.

The separator incorporated in the lithium battery has a function of suppressing an increase in the short-circuit current by closing the pores of the separator by melting the resin at the time of abnormal heat generation and decreasing the ionic conductivity. . However, the separator at a location away from the heat generating portion does not always melt, and there is a possibility that a short circuit may occur due to the separator contracting due to heat. Thus, the means for preventing heat generation due to internal short circuit still leaves room for improvement.

In order to solve the problem of internal short circuit, in Patent Document 1, a CC foil (carbon coat) having a PTC function in which a resin layer to which conductive particles are added using a fluororesin or an olefin resin as a binder is formed on a conductive substrate. Foil) has been proposed. Patent Document 2 discloses a PTC layer in which carbon black is added to a polymer (for example, polyethylene). Patent Document 3 discloses a resin layer composed of a CC layer (carbon coat layer) having a surface roughness Ra (arithmetic mean roughness) of 0.5 to 1.0 μm.

JP 2001-357854 A Japanese Patent Laid-Open No. 10-241665 JP 2010-212167 A

However, the prior art described in the above literature has room for improvement in the following points.

First, in the PTC layer or the resin layer described in Patent Documents 1 to 3, when the conductive paths are densely formed to increase the conductivity more than necessary, there are few conductive paths that are cut even if the binder expands and melts. . On the other hand, if there are too few conductive paths, there is a problem that the resistance at room temperature is too high and the output characteristics of the battery or power storage component deteriorate.

Second, in the PTC layer or the resin layer described in Patent Documents 1 to 3, the expression of the PTC function is due to the thermal expansion of the binder resin. On the other hand, since the capacity of the battery or the power storage component is increased, there is no room for thermal expansion of the PTC layer or the resin layer because the amount of the active material is increased and the density of the active material layer is also increased.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a current collector having a PTC layer having room for thermal expansion at the time of temperature rise while ensuring sufficient conductivity at a normal temperature.

According to this invention, a collector provided with an electroconductive base material and the resin layer provided in the at least single side | surface of the electroconductive base material is provided. Note that the resin layer includes an organic resin and conductive particles. The amount of the resin layer deposited on the conductive substrate is 0.5 to 20 g / m ² . Further, Rz (ten-point average roughness) of the surface of the resin layer is 0.4 to 10 μm. In addition, the Sm (average interval of irregularities) on the surface of the resin layer is 5 to 200 μm. The average resistance of the resin layer measured by the two-terminal method is 0.5 to 50Ω.

According to this configuration, it is possible to obtain a current collector having a PTC layer having room for thermal expansion when the temperature rises while ensuring sufficient conductivity at a normal temperature.

Also, according to the present invention, there is provided an electrode structure comprising the above-described current collector and an active material layer or an electrode material layer provided on the resin layer of the current collector.

Since this electrode structure includes the above-described current collector, sufficient conductivity can be ensured during normal operation, and a sufficient safety function can be achieved during an internal short circuit.

In addition, according to the present invention, there is provided a nonaqueous electrolyte battery or a power storage component comprising the above current collector and an active material layer or an electrode material layer provided on the resin layer of the current collector. Is done.

Since this non-aqueous electrolyte battery or power storage component includes the above-described current collector, sufficient conductivity can be ensured during normal operation, and a sufficient safety function can be achieved during an internal short circuit.

According to the present invention, it is possible to obtain a current collector having a PTC layer having room for thermal expansion when the temperature rises while ensuring sufficient conductivity at a normal temperature.

It is sectional drawing which showed the structure of the electrode structure which concerns on embodiment. It is sectional drawing for demonstrating the problem of the electrode structure provided with the conventional PTC layer. It is sectional drawing for demonstrating the problem of the electrode structure provided with the conventional PTC layer. It is sectional drawing for demonstrating a point from which the electrode structure which concerns on embodiment differs from the electrode structure provided with the conventional PTC layer. It is sectional drawing which showed the mechanism in which the resistance of the PTC layer of the electrode structure which concerns on embodiment rises rapidly. It is a graph for demonstrating the method of prescribing | mixing the mixing ratio of polypropylene resin and polyethylene resin by the peak which appears in DSC (differential scanning calorimetry).

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. In the present specification, “A to B” means “A or more and B or less”.

<Overall configuration of electrode>
FIG. 1 is a cross-sectional view showing the structure of the electrode structure according to the embodiment. The electrode structure 110 of this embodiment includes a current collector 100. The current collector 100 includes a conductive substrate 102 and a resin layer 103 provided on at least one surface of the conductive substrate 102. The electrode structure 110 of the present embodiment further includes an active material layer (or electrode material layer) 105 provided on the resin layer 103 of the current collector 100. The resin layer 103 has a roughened surface 109 as will be described later.

<Problems of conventional PTC layer>
FIG. 2 is a cross-sectional view for explaining problems of an electrode structure having a conventional PTC layer. In the electrode structure 210 having the conventional PTC layer 203, if the conductive paths 211 are too small, there is a problem that the resistance at the normal temperature is too high and the output characteristics of the battery or the power storage component are deteriorated.

That is, as shown in FIG. 2, if the conductive path 211 is too small, the conductive path 211 is easily cut when the binder resin 207 of the PTC layer 203 is thermally expanded (when the film thickness of the PTC layer 203 is increased). In addition, it provides a sufficient safety function when an internal short circuit occurs. However, there is a problem that the resistance of the PTC layer 203 at room temperature is too high and sufficient conduction cannot be obtained between the conductive base material 202 and the active material layer 205.

FIG. 3 is a cross-sectional view for explaining problems of an electrode structure having a conventional PTC layer. In the electrode structure 310 including the conventional PTC layer 303, when the conductive paths 311 are formed densely and the conductivity is increased more than necessary, there are few conductive paths 311 that are cut even when the binder resin 307 expands and melts. There is.

That is, as shown in FIG. 3, when the number of conductive paths 311 is increased too much, sufficient resistance is obtained between the conductive substrate 302 and the active material layer 305 because the resistance of the PTC layer 303 is low at room temperature. However, when the binder resin 307 of the PTC layer 303 is thermally expanded (when the film thickness of the PTC layer 303 is increased), the conductive path 211 is difficult to be cut, so that there is a problem that a sufficient safety function cannot be exhibited during an internal short circuit.

Also, in an electrode structure having a conventional PTC layer, the PTC function is manifested by thermal expansion of the binder resin. On the other hand, since the capacity of the battery or the power storage component is increased, there is a problem that there is no room for thermal expansion of the PTC layer because the amount of the active material is increased and the density of the active material layer is increased.

<Roughened surface of resin layer>
FIG. 4 is a cross-sectional view for explaining a difference between the electrode structure according to the embodiment and a conventional electrode structure including a PTC layer. As already described, the electrode structure 110 according to the present embodiment includes the conductive substrate 102 and the resin layer 103 provided on at least one surface of the conductive substrate 102. The resin layer 103 has a roughened surface 109 as will be described later. The electrode structure 110 of the present embodiment further includes an active material layer (or electrode material layer) 105 provided on the resin layer 103. The active material layer 105 includes an active material 121, a conductive material 123, and a binder 125.

The resin layer 103 includes an organic resin 107 and conductive particles 111. The amount of the resin layer 103 attached to the conductive substrate 102 is 0.5 to 20 g / m ² . The Rz (ten-point average roughness) of the roughened surface 109 of the resin layer 103 is 0.4 to 10 μm. In addition, the Sm (average interval of unevenness) of the roughened surface 109 of the resin layer 103 is 5 to 200 μm. The average resistance of the resin layer 103 measured by the two-terminal method is 0.5 to 50Ω.

FIG. 5 is a cross-sectional view illustrating a mechanism in which the resistance of the PTC layer of the electrode structure according to the embodiment rapidly increases. When this electrode structure 110 is used, when the temperature in the nonaqueous electrolyte battery or the power storage component reaches the vicinity of the melting point of the organic resin 107, the organic resin 107 expands in volume and is dispersed in the resin layer 103. The conductivity is lowered because the contact between the particles 111 is peeled off.

And since the electrode structure 110 of this embodiment has the resin layer 103 which has the special roughening surface 109, it is in securing moderate space on the resin layer 103 surface as a room of thermal expansion of the resin layer 103. Has succeeded. Therefore, even if the volume change at the time of melting of the organic resin 107 is large, it can be thermally expanded without any problem, and good PTC characteristics can be obtained. That is, when the internal temperature of the nonaqueous electrolyte battery or the power storage component reaches the vicinity of the melting point of the organic resin 107 due to heat generated when the nonaqueous electrolyte battery or the power storage component is overcharged, the resistance of the resin layer 103 rapidly rises and becomes conductive. The electric current between the conductive substrate 102 and the active material layer 105 is interrupted. Therefore, if this electrode structure 110 is used, a sufficient safety function can be exhibited at the time of an internal short circuit of the nonaqueous electrolyte battery or the power storage component.

That is, according to this configuration, it is possible to obtain the electrode structure 110 that simultaneously exhibits a good balance between the two effects of ensuring sufficient electrical conductivity at normal temperatures and having room for thermal expansion when the temperature rises. These two effects are difficult to achieve at the same time in the

conventional electrode structures

210 and 310 described with reference to FIGS. On the other hand, since the electrode structure 110 of the present embodiment has the resin layer 103 having the special roughened surface 109, it has succeeded in satisfying these two conflicting effects at the same time.

Hereinafter, each component will be described in detail.

<Conductive substrate>
As the conductive substrate 102 of the present embodiment, various metal foils for nonaqueous electrolyte batteries or power storage components can be used. Specifically, various metal foils for the positive electrode and the negative electrode can be used. For example, aluminum, copper, stainless steel, nickel and the like can be used. Among these, aluminum and copper are preferable from the balance between high conductivity and cost. In this specification, aluminum means aluminum and an aluminum alloy, and copper means pure copper and a copper alloy. In the present embodiment, the aluminum foil can be used on the secondary battery positive electrode side, the secondary battery negative electrode side or the electric double layer capacitor electrode, and the copper foil can be used on the secondary battery negative electrode side. Although it does not specifically limit as aluminum foil, Various things, such as A1085 material which is a pure aluminum type, and A3003 material, can be used. Moreover, it is the same also as copper foil, Although it does not specifically limit, Rolled copper foil and electrolytic copper foil are used preferably.

The thickness of the conductive substrate 102 is not particularly limited, but is preferably 5 μm or more and 50 μm or less. If the thickness is less than 5 μm, the strength of the foil may be insufficient and it may be difficult to form the conductive substrate 102 or the like. On the other hand, if it exceeds 50 μm, the other constituent elements, particularly the active material layer 105 or the electrode material layer, must be thinned. In particular, when the power storage component such as a nonaqueous electrolyte battery or a power storage component is used, the active material layer In some cases, the thickness of 105 must be reduced, and a necessary and sufficient capacity cannot be obtained.

<Resin layer>
The resin layer 103 of the present embodiment is a PTC (Positive temperature coefficient) layer including an organic resin 107 and conductive particles 111 laminated on the surface of the conductive substrate 102.

(1) Structure of roughened surface The adhesion amount of the resin layer 103 of the present embodiment on the conductive substrate 102 is 0.5 to 20 g / m ² . If it is less than 0.5 g / m < ² >, an uncoated part will generate | occur | produce and battery performance or electrical storage performance will run short. When it exceeds 20 g / m ² , the resistance is too large and the battery performance or the power storage performance is insufficient. The adhesion amount of the resin layer 103 may be, for example, 0.5, 1, ^{2, 5} , 10, 15, 20 g / m ² , and is within a range between any two of the numerical values exemplified here. May be.

The Rz (ten-point average roughness) of the roughened surface 109 of the resin layer 103 of the present embodiment is 0.4 to 10 μm. If Rz is less than 0.4 μm, there is insufficient room for thermal expansion. When Rz exceeds 10 μm, the contact with the active material layer 105 is poor, and the contact battery performance or the contact storage performance is insufficient. Rz of the resin layer 103 may be 0.4, 0.7, 1, 2, 5, 10 μm, for example, or may be within a range between any two of the numerical values exemplified here.

Sm (average interval of irregularities) of the roughened surface 109 of the resin layer 103 of the present embodiment is preferably 5 to 200 μm. If Sm is less than 5 μm, there is insufficient room for thermal expansion. If Sm exceeds 200 μm, the surface shape is too flat and there is insufficient room for thermal expansion. The Sm of the resin layer 103 may be, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200 μm, and is exemplified here. It may be within a range between any two of the numerical values.

The average resistance measured by the two-terminal method of the resin layer 103 of this embodiment is 0.5 to 50Ω. If the average resistance is within this range, it is possible to avoid the problem that the conductive path is cut off due to the expansion of the organic resin 107 due to the temperature rise in the temperature range lower than the temperature to be shut down, and the conductive path can be connected at the last minute. . Specifically, the initial resistance of the resin layer 103 is a resistance value measured by Mitsubishi Analitech's resistivity meter Loresta EP (two-terminal method) (measured from above the resin layer 103 formed on the conductive base material 102) of 0.5 to 50Ω. If it is. If it is less than 0.5Ω, the resistance rise at the time of temperature rise is insufficient. When it exceeds 50Ω, the performance as a battery or a storage battery is insufficient.

The resin used as the organic resin 107 of the resin layer 103 is not particularly limited, but is selected from the group consisting of a fluorine resin, an olefin resin, an epoxy resin, an acrylic resin, a polyester resin, and a urethane resin. More than seeds can be used. Among these, it is particularly preferable to use a fluorine resin or an olefin resin.

(2) Fluorine-based resin The fluorine-based resin used as the organic resin 107 of the resin layer 103 is a resin containing a fluorine resin as a resin component, and may be composed of only a fluorine resin. It may contain a resin. The fluororesin is a resin containing fluorine, such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer. Fluororesins such as coalescence (FEP), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF); Examples thereof include fluorine copolymers obtained by copolymerizing cyclohexyl vinyl ether or carboxylic acid vinyl ester with fluoroolefins such as PCTFE and tetrafluoroethylene. These can be used singly or in combination of two or more, but polyvinylidene fluoride (PVDF) is particularly preferable in that it can reliably combine a shutdown function and excellent high rate characteristics.

The fluororesin can be used in an amount of 100% by mass when the entire resin component is 100% by mass, but can also be used in combination with other resin components. It is preferable to contain 40 mass% or more normally with respect to all the resin components, Preferably it contains 50 mass% or more. This is because if the blending amount of the fluororesin is too small, control of the conductive particles described later will not be successful, and it will be difficult to reliably combine a shutdown function and excellent high rate characteristics. Specifically, the ratio of the fluororesin is, for example, 40, 50, 60, 70, 80, 90, 100% by mass, and may be within the range of any two numerical values exemplified here.

The weight average molecular weight of the fluororesin is, for example, 30,000 to 1,000,000, specifically, for example, 30,000, 40,000, 50,000, 60,000, 80,000, 90,000, 100,000, 150,000. , 200,000, 300,000, 400,000, 500,000, 700,000, 800,000, 900,000, 1 million, and may be in the range between any two of the numerical values exemplified here. A weight average molecular weight means what was measured by GPC (gel permeation chromatograph).

The fluororesin preferably has a carboxyl group or a carboxylic ester group (hereinafter simply referred to as “ester group”). This is because the adhesion between the conductive substrate 102 and the resin layer 103 can be improved. Further, when the fluororesin has an ester group, the adhesion between the fluororesin and conductive particles (eg, carbon particles) is improved.

The embodiment in which the fluororesin has a carboxyl group (—COOH) or an ester group (—COOR, R is, for example, a hydrocarbon having 1 to 5 carbon atoms) is not particularly limited. For example, the fluororesin is a carboxyl group or an ester. It may be a copolymer of a monomer having a group and a monomer containing fluorine, and the fluororesin may be a mixture of a fluororesin and a resin having a carboxyl group or an ester group. The resin may be modified with a compound having a carboxyl group or an ester group. The method for modifying the fluororesin is not particularly limited, but in one example, as disclosed in JP-A-2002-304997, radiation is emitted to the fluororesin to desorb fluorine atoms to generate radicals. And the method of graft-polymerizing the compound which has a carboxyl group or an ester group on a fluororesin by mixing a fluororesin and the compound which has a carboxyl group or an ester group in that state is mentioned. The value of the ratio of the number of carboxyl groups or ester groups to the number of fluorine atoms in the fluorine-based resin is not particularly limited, but is, for example, 0.1 to 5, and preferably 0.5 to 2. The value of this ratio is specifically, for example, 0.1, 0.2, 0.5, 1, 1.5, 2, 3, 4, 5, and between any two of the numerical values exemplified here. It may be within the range. Examples of the monomer (or compound) having a carboxyl group or an ester group include acrylic acid, methacrylic acid, and esters thereof (eg, methyl methacrylate).

(3) Olefin resin The olefin resin used as the organic resin 107 of the resin layer 103 is a resin containing an olefin resin as a resin component, and may be composed of only an olefin resin. It may contain a resin. Examples of the olefin resin include polyethylene, polypropylene, polybutene, polystyrene and the like. These can be used singly or in combination of two or more, but polyethylene and polypropylene are particularly preferable in that they can surely have both a shutdown function and excellent high rate characteristics.

When the total resin component is 100% by mass, this olefinic resin can be used in an amount of 100% by mass, but can also be used in combination with other resin components. It is preferable to contain 40 mass% or more normally with respect to all the resin components, Preferably it contains 50 mass% or more. This is because if the blending amount of the olefin resin is too small, control of conductive particles described later will not be successful, and it will be difficult to reliably combine a shutdown function and excellent high rate characteristics. Specifically, the ratio of the olefin resin is, for example, 40, 50, 60, 70, 80, 90, 100% by mass, and may be within the range of any two numerical values exemplified here.

The weight average molecular weight of the olefin resin is, for example, 10,000 to 1,000,000, specifically, for example, 10,000, 30,000, 40,000, 50,000, 60,000, 80,000, 90,000, 100,000. 150,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, 1 million, and within the range between any two of the numerical values exemplified here Also good. A weight average molecular weight means what was measured by GPC (gel permeation chromatograph).

This olefin resin is preferably modified with carboxylic acid or the like to have a carboxyl group or a carboxylic ester group (hereinafter simply referred to as “ester group”). This is because the adhesion between the conductive substrate 102 and the resin layer 103 can be improved. Moreover, when an olefin resin has an ester group, the adhesiveness of an olefin resin and electroconductive particle (example: carbon particle) improves. The carboxylic acid for modifying the olefinic resin may be any of monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. For example, acetic acid, acetic anhydride, maleic acid, maleic anhydride, trimellitic acid, trimellitic anhydride, Fumaric acid, adipic acid, glutaric acid, succinic acid, malonic acid, oxalic acid and the like can be used. This is because the more carboxyl group, the better the adhesion to the conductive substrate, but the dispersibility of the conductive particles may be lowered and the resistance may be increased.

In addition, it is preferable to make this olefin resin into a copolymer with acrylic acid ester and methacrylic acid ester. The acrylic ester and methacrylic ester preferably further have a glycidyl group. By containing acrylic acid ester and methacrylic acid ester, the adhesion to the conductive substrate is improved and the capacity retention rate is improved. By having the glycidyl group, the adhesion is further improved, and the capacity retention rate is improved.

The olefin resin is preferably a mixture of a polypropylene resin and a polyethylene resin. As shown in FIG. 6, the mixing ratio of the polypropylene resin and the polyethylene resin is defined by a peak appearing in DSC (differential scanning calorimetry). This is because simply adding a predetermined amount of polypropylene-based resin and polyethylene-based resin may change the crystal state and the like, and a desired result may not be obtained. When DSC measurement of a coating film using a polypropylene resin and a polyethylene resin is performed, a peak due to thermal melting appears on the temperature rising side. A coating film made of a mixed system of a polypropylene resin and a polyethylene resin and a conductive material is thermally analyzed by DSC and melted from the melting peak area of each resin (the area surrounded by the thermal melting peak and straight line of each resin). The amount of heat is determined, and the ratio of addition is defined by the ratio of the heat of fusion of each resin to the heat of fusion of both. Specifically, the addition ratio of the polypropylene resin is (the heat of fusion of the polypropylene resin) / (the heat of fusion of the polypropylene resin + the heat of fusion of the polyethylene resin) × 100 (%), and this ratio is 95% to 30%. % Is preferred.

(4) Conductive Particles As the conductive particles 111 used in the resin layer 103 of the present embodiment, known conductive fine particles such as carbon powder and metal powder can be used, among which furnace black, acetylene black, and ketjen. Carbon black such as black is preferred. In particular, it is preferable that the electrical resistance of the powder is 100% green compact and 1 × 10 ⁻¹ Ω or less, and the above can be used in combination as necessary. The particle size is not particularly limited, but the primary particle size is preferably about 10 to 100 nm.

The blending amount of the conductive particles 111 is not particularly limited, but is preferably blended so that the volume% value occupied by the conductive particles 111 is 5 to 50% when the entire resin layer 103 is 100%. . If the blending amount of the conductive particles 111 is too small, the number of contact points between the conductive particles 111 is small, and the electrical resistance at normal temperature is increased. When there are too many compounding quantities of the electroconductive particle 111, the contact between the electroconductive particles 111 will be maintained also at the time of temperature rising, and it will become difficult to exhibit a shutdown function. This value is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50%, and may be within a range between any two of the numerical values exemplified here.

(5) Method for Producing Roughened Surface The surface shape (surface roughness) of the roughened surface 109 of the resin layer 103 of this embodiment is obtained by dispersing the conductive particles 111 by a predetermined dispersion method, and further by predetermined baking conditions. It is obtained by coating with.

The dispersion state of the conductive particles 111 of the present embodiment is realized by the following dispersion method, for example. Conventionally, the dispersion of the conductive material has been carried out mainly with the aim of finely and evenly dispersing, but in this embodiment, a suitably agglomerated dispersion state is preferable, and the method will be described below. Dispersers, planetary mixers, ball mills, and the like can be used as the dispersers. Hereinafter, the case where a disperser is used will be described.

The dispersion state of the conductive particles 111 of the present embodiment can be achieved, for example, by pre-dispersing the conductive particles 111 in a solution of a fluorine-based resin or an olefin-based resin, and further performing this dispersion. In the preliminary dispersion, a conductive material is added to the resin liquid so that the concentration of the conductive material in the solid content (resin solid content + conductive material) is 10 to 70% by volume, and 2 to 60 at a rotational speed of 300 to 5000 rpm. A pre-dispersed paint is produced by stirring for a minute. In this specification, it is calculated by volume part (ml) = mass part (g) / true specific gravity, and volume% is calculated based on the calculation. If the amount of conductive particles in the pre-dispersion is less than 10% by volume, the particle size after the main dispersion may become too small, and if it exceeds 70% by volume, the particle size after the main dispersion may become too large. If the rotation speed of the preliminary dispersion is lower than 300 rpm, the particle diameter after the main dispersion may become too large, and if it exceeds 5000 rpm, the particle diameter after the main dispersion may become too small. If the pre-dispersion stirring time is shorter than 2 minutes, the particle size after the main dispersion may become too large, and if longer than 60 minutes, the particle size after the main dispersion may become too small.

Thereafter, in this dispersion, the resin solution is added to the pre-dispersion paste so that the conductive material addition amount in the resin layer is 5 to 50% by volume (the solid content in the resin liquid (resin solid content + conductive material)). So that the concentration of the conductive material is 5 to 50% by volume). In this dispersion, stirring is performed at a rotational speed of 500 to 8000 rpm for 10 to 120 minutes. If the rotational speed of this dispersion is lower than 500 rpm, the particle size may be too large, and if it is higher than 8000 rpm, the particle size may be too small. If the stirring time of this dispersion is shorter than 10 minutes, the particle size may be too large, and if longer than 120 minutes, the particle size may be too small.

The method for manufacturing the current collector 100 of the present embodiment is not particularly limited as long as the resin layer 103 is formed on the conductive base material 102 by a known method. It is also effective to perform a pretreatment so that the adhesiveness of the conductive substrate 102 is improved. In particular, when using a metal foil produced by rolling, rolling oil or wear powder may remain, and adhesion with the resin layer may deteriorate. In this case, rolling oil or wear powder By removing degreasing by degreasing or the like, adhesion with the resin layer 103 can be improved. Also, the adhesion with the resin layer 103 can be improved by a dry activation treatment such as a corona discharge treatment.

There is no particular limitation on the method of applying the above paste containing the conductive material 111, but a known method such as a casting method, a bar coater method, a dip method, or a gravure coating method can be used. There is no restriction | limiting in particular also about the drying method, Drying by the heat processing in a hot-air circulation furnace, etc. can be used.

<Active material layer>
The electrode structure 110 of the present embodiment includes an active material layer 105 including an active material, which is laminated on the resin layer 103. Since the electrode structure 110 includes the active material layer 105 containing the active material particles 121 on the current collector 100, good discharge rate characteristics can be obtained.

The electrode structure 110 of this embodiment can be obtained by forming an active material layer or an electrode material layer on at least one surface of the current collector 100 of this embodiment. The electrode structure for an electrical storage component in which the electrode material layer is formed will be described later. First, in the case of the electrode structure 110 in which the active material layer 105 is formed, an electrode structure for a nonaqueous electrolyte battery, for example, a lithium ion secondary battery (for example, a lithium ion secondary battery) using the electrode structure 110 and a separator, a nonaqueous electrolyte solution, or the like ( Battery components). In the electrode structure 110 for a non-aqueous electrolyte battery and the non-aqueous electrolyte battery of the present embodiment, a member other than the current collector 100 can be a known non-aqueous battery member.

Here, the active material layer 105 formed as the electrode structure 110 in the present embodiment may be conventionally proposed for a non-aqueous electrolyte battery. For example, the current collector 100 of the present embodiment using aluminum as the positive electrode, LiCoO ₂ , LiMnO ₂ , LiNiO ₂ or the like as the active material 121, carbon black such as acetylene black as the conductive particles 123, etc. The positive electrode structure of this embodiment can be obtained by applying and drying a paste dispersed in PVDF or water-dispersed PTFE as the binder 125.

When the negative electrode structure 110 is used, for example, graphite, graphite, mesocarbon microbeads or the like are used as the active material 121 for the current collector 110 of the present embodiment using copper as the conductive substrate 102, and these are increased. The negative electrode structure of the present embodiment can be obtained by coating and drying a paste mixed with SBR as a binder after being dispersed in CMC as a sticking agent as a material for forming the active material layer 105.

As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.

<Formation of resin layer on conductive substrate>
Based on Table 1, coating amounts using various resins were prepared. As the olefin resin, an aqueous emulsion having a solid content of 5 to 40% by weight was used. The mixture of polypropylene and polyethylene in Example 18 was mixed so that the addition ratio of polypropylene was 50% based on the DSC chart of the coating film.

The PVDF resin used was an N-methyl-2-pyrrolidone solution having a solid content of 10 to 15% by weight. As the epoxy resin, a bisphenol A type resin and a urea resin dissolved in methyl ethyl ketone at a solid content of 20% by weight were used. As the polyester resin, a polyester resin produced by an esterification reaction of isophthalic acid and ethylene glycol and dissolved in xylene at a solid content of 20% by weight was used. As the urethane resin, a urethane resin obtained by reacting isophorone diisocyanate and polyethylene glycol and butylated melamine dissolved in xylene at a solid content of 20% by weight was used. As the acrylic resin, an aqueous emulsion having a solid content of 20% by weight of a copolymer of butyl acrylate, acrylonitrile, and acrylamide was used. All molecular weights were measured by GPC (gel permeation chromatography) in the state of a resin solution. The paste obtained by pre-dispersion and main dispersion based on Table 2 was applied to an aluminum foil and baked at a baking temperature (base material arrival temperature) of 100 ° C. and a baking time (in-furnace time) of 120 seconds. A CC layer (carbon coat layer) was formed on the foil.

In Tables 1 to 3 below, the meaning of each abbreviation is as follows.
AB: Acetylene black PP: Polypropylene PE: Polyethylene PEO: Polyethylene oxide PVDF: Polyvinylidene fluoride

<Evaluation method>
(1) Amount of coating The coated foil was cut into 100 mm squares, and the mass was measured. After removing the coating film, the mass was measured again, and the adhesion amount was calculated from the difference. Table 3 shows the measurement results.
(2) Roughness measurement Measured with a rough clock (SE-30D manufactured by Kosaka Laboratory) (reference length 2.5 mm, cut-off λc 0.8 mm, drive speed 0.1 mm / s). Based on JIS B0601, Rz (ten-point average roughness) and Sm (average interval of unevenness) were measured. Table 3 shows the measurement results (average of n = 5).

(3) Resistance The initial resistance was measured from the top of the CC layer (carbon coat layer) formed on the aluminum foil as a resistance value by Loresta EP (two-terminal method) manufactured by Mitsubishi Chemical Analytech. Table 3 shows the measurement results (average of n = 10).

(4) Capacity maintenance rate (4-1) Battery production (4-1-1) Production of positive electrode An active material paste (LiMn ₂ O ₄ / AB / PVDF = 89.5 / 5 / 5.5, solvent NMP (N-methyl-2-pyrrolidone)) was applied and dried. Further, pressing was performed to form an active material layer having a thickness of 60 μm.

(4-1-2) Production of Negative Electrode An active material paste (MCMB (mesocarbon microbeads) / AB / PVDF = 93/2/5, solvent NMP) was applied to a 10 μm thick copper foil and dried. Further, pressing was performed to form an active material layer having a thickness of 40 μm.

(4-1-3) Production of Cylindrical Lithium Ion Battery This positive electrode, negative electrode, electrolyte (1M LiPF ₆ , EC (ethylene carbonate) / MEC (methyl ethyl carbonate) = 3/7), separator (thickness 25 μm, A microporous polyethylene film) was wound, a lead was welded to each electrode, connected to each electrode terminal, and inserted into a case to obtain a cylindrical lithium ion battery (φ18 mm × axial length 65 mm).

(4-2) Capacity maintenance rate measurement (high rate characteristics)
Using this cylindrical lithium ion battery, after constant current and constant voltage charging to 4.2V at 0.25 mA / cm ^2, a constant current discharge at 0.25 mA / cm ² and 5 mA / cm ^2, each of the discharge From the capacity, discharge retention ratio = (discharge capacity of 5 mA / cm ² ) / (discharge capacity of 0.25 mA / cm ² ) was calculated. If the capacity maintenance rate is 0.8 or more, it can be used at a high rate. Table 3 shows the measurement results.

(4-3) Overcharge test Using the above-described cylindrical lithium ion battery, after charging with constant current and constant voltage at a charging voltage of 1.5 mA / cm ² up to 4.2 V, the battery was further charged with a fully charged cylindrical lithium ion battery. The battery was charged with 5A until it reached% charge, and the behavior of the cylindrical lithium ion battery was investigated. Table 3 shows the measurement results.

<Consideration of results>
In Examples 1 to 18, the capacity maintenance ratio measurement (high rate characteristic) was 0.80 or more, and the result of the overcharge test was good with no change in the battery. The capacity maintenance rate measurement (high rate characteristic) is less than 0.80 or the overcharge test result is smoke (a state where the shutdown function is insufficient and smoke is emitted from the battery), which is not suitable for practical use. Therefore, in Examples 1 to 18, since the CC layer (carbon coat layer) having a special roughened surface is provided, the CC layer (carbon coat layer) is used as a room for thermal expansion of the CC layer (carbon coat layer). It has succeeded in securing an appropriate space on the surface. Therefore, even if the volume change at the time of melting | dissolving of various organic resin is large, it can be understood that it can expand | swell without a problem and can obtain a favorable PTC characteristic.

In the above, this invention was demonstrated based on the Example. It is to be understood by those skilled in the art that this embodiment is merely an example, and that various modifications are possible and that such modifications are within the scope of the present invention.

DESCRIPTION OF SYMBOLS 100 Current collector 102 Conductive base material 103 Resin layer 105 Active material layer 107 Organic resin 109 Roughening surface 110 Electrode structure 111 Conductive particle 121 Active material 123 Conductive material 125 Binder 202 Conductive base material 203 PTC layer 205 Active Material layer 207 Binder resin 210 Electrode structure 211 Conductive path 302 Conductive base material 303 PTC layer 305 Active material layer 307 Binder resin 310 Electrode structure 311 Conductive path

Claims

A conductive substrate;
A resin layer provided on at least one side of the conductive substrate;
A current collector comprising:
The resin layer includes an organic resin and conductive particles,
The amount of adhesion of the resin layer on the conductive substrate is 0.5 to 20 g / m 2 ;
Rz (ten-point average roughness) of the surface of the resin layer is 0.4 to 10 μm,
Sm (average interval of irregularities) on the surface of the resin layer is 5 to 200 μm,
The average resistance measured by the two-terminal method of the resin layer is 0.5 to 50Ω,
Current collector.
The organic resin is at least one selected from the group consisting of a fluorine resin, an olefin resin, an epoxy resin, an acrylic resin, a polyester resin, and a urethane resin.
The current collector according to claim 1.
The fluororesin has a carboxyl group or a carboxylic acid ester;
The current collector according to claim 2.
The olefin resin has a carboxyl group or a carboxylic ester.
The current collector according to claim 2.
The olefin resin contains at least one acrylic ester or methacrylic ester,
The current collector according to claim 2.
The olefin resin includes a polypropylene resin and a polyethylene resin,
The current collector according to claim 2.
A current collector according to any one of claims 1 to 6;
An active material layer or an electrode material layer provided on the resin layer of the current collector;
An electrode structure comprising:
A current collector according to any one of claims 1 to 7;
An active material layer or an electrode material layer provided on the resin layer of the current collector;
A non-aqueous electrolyte battery or a power storage component.